CN103534318A - Conductive polymer suspension and method for producing same, conductive polymer material, and electrolytic capacitor and method for producing same - Google Patents
Conductive polymer suspension and method for producing same, conductive polymer material, and electrolytic capacitor and method for producing same Download PDFInfo
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- CN103534318A CN103534318A CN201280023696.9A CN201280023696A CN103534318A CN 103534318 A CN103534318 A CN 103534318A CN 201280023696 A CN201280023696 A CN 201280023696A CN 103534318 A CN103534318 A CN 103534318A
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- Prior art keywords
- conductive polymer
- electric conductive
- suspension
- polymer suspension
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- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
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- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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Abstract
In the present invention, a conductive polymer suspension is produced by subjecting a monomer that forms a conductive polymer to chemical oxidation polymerization using an oxidizer and recovering the conductive polymer in a solvent containing an organic acid or salt thereof as the dopant; exposing the conductive polymer to an oxidizer in an aqueous solvent containing a poly acid; further adding a dispersant having a branched structure; and then pulverizing the conductive polymer. Using this conductive polymer suspension, it is possible to provide an organic material having high conductivity and excellent substrate adhesion and water resistance and a method for producing the same, as well as an electrolytic capacitor and method for producing the same.
Description
Technical field
According to embodiment of the present invention, relate to a kind of electric conductive polymer suspension and a kind of method for the preparation of suspension, the conductive polymer material being obtained by described suspension, and a kind of a kind of electrolytic condenser and method for the preparation of described electrical condenser of using described material.
Background technology
Conductive polymer material is used to the electrode of electrical condenser, the electrode of dye sensitization solar battery, the electrode of electroluminescent display.As this conductive polymer material, known by one or more monomers of polymerization as pyrroles, thiophene, 3,4-Ethylenedioxy Thiophene, the polymer materials that aniline obtains, and correlation technique is disclosed in patent documentation 1 to 3.
Reference listing
Patent documentation
Patent documentation 1:JP07-090066A
Patent documentation 2:JP2004-059666A
Patent documentation 3:JP2004-305086A
Summary of the invention
Technical problem
Yet, under the existence of polyanion of serving as doping agent 3, in the method for the oxidation chemistry polymerization of 4-dialkoxythiophene, because be difficult to controlled doping rate, neither as doping agent, use the polyanion also do not contribute to electric conductivity to exist with excessive.Therefore the method that, is difficult in patent documentation 1 and 2 to describe is enough to as for the preparation of the method with the polymer materials of high conductivity.
In addition, the surface resistivity of antistatic material is categorized as 10 conventionally
5to 10
14Ω/sq and electric conductivity are (lower than 10
5Ω/sq) too high and may occur serious static discharge.What therefore, consider is that this antistatic material does not have electric conductivity promptly to disperse the static of charged object.Even if antistatic material has the enough electric conductivitys as antistatic material, when using this antistatic material to be used for, for example, during the electrode of electrical condenser, aspect electric conductivity, be difficult to meet fully the needs for low ESR.In addition, the excessive conductive polymer material that comprises polyanion non-constant in water tolerance, and, therefore, using this conductive polymer material is disadvantageous for electrolytical electrical condenser, because it is in reliability, especially the performance under high humidity atmosphere is not enough.
In the method for describing in patent documentation 3, the particle diameter of the polystyrolsulfon acid particle of 90 % by weight in dispersion liquid and the poly-Ethylenedioxy Thiophene particle of 3,4-is set as to 50nm following to increase resistance so that dispersion liquid is suitable for the hole-input horizon of electroluminescent device.Therefore the coating agent of, being made by dispersion liquid is at electric conductivity (>5000 Ω cm; Be less than 2 * 10
-4s/cm) upper low.Therefore,, about patent documentation 1 and 2, when using this coating agent for the electrode of for example electrical condenser, aspect electric conductivity, be difficult to fully meet the needs for low ESR.
According to the target of embodiment of the present invention, be in order to overcome the above problems, and be provided for providing the electric conductive polymer suspension of polymer materials high in electric conductivity and for the preparation of the method for suspension, and provide low and in reliability on ESR, especially, outstanding electrolytic condenser in nature under high humidity atmosphere, and for the preparation of the method for electrical condenser.
The mode of dealing with problems
According to embodiment of the present invention, relate to a kind of electric conductive polymer suspension, described electric conductive polymer suspension comprises electric conductive polymer, at least one polyanion, and at least one has the dispersion agent of branched structure.
According to embodiment of the present invention, relate to a kind of electric conductive polymer suspension, wherein the particle diameter of electric conductive polymer is partly or wholly below 100nm.
According to embodiment of the present invention, relate to a kind of method for the preparation of electric conductive polymer suspension, described method comprises:
First step, by using oxygenant to for providing the monomer of electric conductive polymer to carry out chemical oxidising polymerisation in containing organic acid or the solvent of its salt as doping agent, so that the mixture that contains electric conductive polymer to be provided,
Second step, reclaims described electric conductive polymer from described mixture,
Third step mixes with described electric conductive polymer oxygenant in containing the aqueous solvent of polyanion, and
The 4th step, mixes and has the dispersion agent of branched structure and afterwards described electric conductive polymer carried out to efflorescence.
According to embodiment of the present invention, relate to a kind of electric conductive polymer suspension, described electric conductive polymer suspension obtains by above method.
According to embodiment of the present invention, relate to a kind of conductive polymer material, described conductive polymer material is by being dried above electric conductive polymer suspension to form to remove solvent.
According to embodiment of the present invention, relate to a kind of electrolytic condenser, described electrolytic condenser comprises dielectric substrate, and described dielectric substrate comprises above electric conductive polymer suspension or above conductive polymer material.
According to embodiment of the present invention, relate to a kind of method for the preparation of electrolytic condenser, described method comprises:
On the surface of the plate conductor that comprises valve metal, form the step of dielectric layer, and
With above electric conductive polymer suspension, be coated with or flood described dielectric layer to form the step of dielectric substrate on described dielectric layer.
According to embodiment of the present invention, relate to a kind of method for the preparation of electrolytic condenser, described method comprises:
On the surface of the plate conductor that comprises valve metal, form the step of dielectric layer,
To for providing the monomer of the first electric conductive polymer compound to carry out chemical oxidising polymerisation or electropolymerization to form the step of the first electric conductive polymer compound layer on described dielectric layer, and
With above-mentioned electric conductive polymer suspension, be coated with or flood described the first electric conductive polymer compound layer to form the step of the second electric conductive polymer compound layer on described the first electric conductive polymer compound layer.
Invention effect
According to according to embodiment of the present invention, can obtain a kind of electric conductive polymer suspension, it is high that described electric conductive polymer suspension is used for providing in electric conductivity, and on to the adhesivity of base material and water tolerance outstanding organic materials.In addition, according to according to embodiment of the present invention, can obtain on ESR low, and outstanding in reliability, especially, outstanding electrolytic condenser in the performance under high humidity atmosphere.
Accompanying drawing summary
[Fig. 1] is that example is according to the schematic section of the structure of the solid electrolytic capacitor of embodiment of the present invention.
Embodiment explanation
Hereinafter, to describe in detail according to a kind of electric conductive polymer suspension of embodiment of the present invention and a kind of conductive polymer material being obtained by this suspension, for the preparation of a method for electric conductive polymer suspension, and a kind of a kind of electrolytic condenser and method for the preparation of electrical condenser of using described conductive polymer material.
<electric conductive polymer suspension and electroconductibility organic materials>
According to the electric conductive polymer suspension of embodiment of the present invention, contain electric conductive polymer, at least one polyanion, and at least one has the dispersion agent of branched structure.
According to above composition, outstanding in the dispersion of particles stability that electric conductive polymer suspension contains therein.Therefore, can reduce the polyanion that does not use and therefore do not contribute to electric conductivity as doping agent with respect to electric conductive polymer.Therefore the conductive polymer material, being obtained by electric conductive polymer suspension can be high in electric conductivity.In addition, because the inexcessive polyanion that contains of electric conductive polymer suspension, the conductive polymer material being obtained by electric conductive polymer suspension is outstanding in water tolerance, and use conductive polymer material to be used for electrolytical electrical condenser in reliability, especially, outstanding in the performance under high humidity atmosphere.
In order to obtain above effect, need polyanion and there is the synergy between the dispersion agent of branched structure.In the situation that using polyanion separately, owing to above reason, the conductive polymer material that existence wherein obtained may situation low and deficiency in water tolerance in electric conductivity.In the situation that use and have the dispersion agent of branched structure separately, because there is not the polyanion that can adulterate with electric conductive polymer, the electroconductibility organic materials obtaining is low in electric conductivity.In addition, in the situation that polyanion and the dispersion agent with linear chain structure, because can not obtain the wherein situation of particle required dispersion stabilization in electric conductive polymer suspension, the dispersion agent that needs polyanion and have a linear chain structure is with respect to the relatively large combination of electric conductive polymer, and therefore exist the conductive polymer material that wherein obtained may be in electric conductivity low and in water tolerance not enough situation.
Above effect is, especially, in the situation that electric conductive polymer suspension contains the electric conductive polymer with the particle diameter below 100nm, that is, therein in the situation that the particle diameter of the electric conductive polymer containing in electric conductive polymer suspension partly or wholly for to represent significantly below 100nm.Conventionally, the particle diameter of the particle in electric conductive polymer suspension is partly or wholly 100nm when following, need to relatively large, contain polyanion so that the dispersion of stabilized particles in electric conductive polymer suspension with respect to electric conductive polymer.Therefore the electroconductibility organic materials, being obtained by electric conductive polymer suspension is low especially in electric conductivity.Yet, according to above composition, even the particle diameter of particle is partly or wholly below 100nm in electric conductive polymer suspension, need to be with the relatively large polyanion that contains yet, and therefore, the electroconductibility organic materials being obtained by electric conductive polymer suspension is high in electric conductivity.
Wherein the particle diameter of electric conductive polymer is partly or wholly for electric conductive polymer suspension below 100nm is suitable for forming conductive polymer material in the hole in the porous material of the plate conductor that comprises valve metal of the mean pore size below having 1000nm.When conductive polymer material is high in electric conductivity, electric conductive polymer suspension is particularly preferred.
The median size of the electric conductive polymer containing in electric conductive polymer suspension (particle) preferably in 1 to 1000nm scope, and more preferably contains the electric conductive polymer with the particle diameter below 100nm as mentioned above therein.
As the electric conductive polymer containing in electric conductive polymer suspension, conductive organic polymer is preferably and comprises pyrroles, thiophene, and at least one the polymkeric substance in their derivative.Its purposes be can depend on and molecular weight and the character of electric conductive polymer selected.When using electric conductive polymer for electrolytic condenser, can select to be suitable for molecular weight and character within the scope of this of composition of electrolytic condenser.As electric conductive polymer, especially, poly-(3, the 4-Ethylenedioxy Thiophene) or derivatives thereof with the structural unit being represented by following formula (1) is preferred.Electric conductive polymer can be homopolymer or multipolymer, also can use its one or more.
With respect to the water that serves as solvent of 100 weight parts, in electric conductive polymer suspension, the content of electric conductive polymer is preferably 0.1 to 30 weight part and more preferably 0.5 to 20 weight part.
Electric conductive polymer suspension contains polyanion.The example of polyanion comprises that poly carboxylic acid is as polyacrylic acid, polymethyl acrylic acid and polymaleic acid; Poly-sulfonic acid is as polyvinylsulfonic acid and polystyrolsulfon acid; And at least one the multipolymer that comprises these structural units.Wherein, the polystyrolsulfon acid comprising by the structural unit of the expression of following (2) is preferred.Can contain one or more this polyanions.
The weight-average molecular weight of polyanion is preferably 2,000 to 500,000 and more preferably 10,000 to 200,000.
Electric conductive polymer suspension preferably contains the dispersion agent with branched structure together with polyanion.Can contain the dispersion agent that one or more have branched structure.
The dispersion agent with branched structure more preferably has the organic polymer dispersion agent of lower array structure, described structure is with and is useful on the adsorption group that is adsorbed to electric conductive polymer in main chain, and described structure is with one or more wetting abilities and/or hydrophobic side chains.
The example of the main chain of dispersion agent comprises polyethylene, polyolefine, polystyrene, polyester, urethane, polymeric amide, polyvinyl acetate, acrylic resin, and the multipolymer that comprises two or more this structural units.
In the main chain of dispersion agent, the example of adsorption group comprises carboxyl, and sulfo group is phosphate-based, and amino.From the angle to the high absorbability of electric conductive polymer, carboxyl and sulfo group are suitable especially.
The example of the side chain of dispersion agent comprises hydrophilic polyethers, polyvinyl alcohol and Polyvinylpyrolidone (PVP), and hydrophobic polyethylene, polyolefine, polystyrene, polyester, urethane, polymeric amide, polyvinyl acetate and acrylic resin.Dispersion agent can contain a side chain, thereby but from obtaining the higher sterically hindered angle that increases the effect of the dispersibility that improves particle, it particularly preferably contains a plurality of side chains.Can there is one or more side chain.Not only from increasing the angle of the stability of particle electric conductive polymer suspension, and from the angle of the intensity of conductive polymer material, dispersion agent particularly preferably contains one or more hydrophilic side chains and one or more hydrophobic side chain simultaneously.
As solids as the dispersion agent of the dispersion agent of pigment in, the dispersion agent with branched structure using can be selected from the dispersion agent with branched structure as above, and, for example, can adopt aptly commercially available dispersion agent, " DISPERBYK-190 " using as each embodiment for describing in the back.
" DISPERBYK-190 " comprises that acrylic resin is as main chain, and main chain with carboxyl as adsorption group." DISPERBYK-190 " as a plurality of side chains, and is the dispersion agent with branched structure with hydrophilic polyethers and hydrophobic polystyrene.
For polyanion in electric conductive polymer suspension and the preferred content with the dispersion agent of branched structure, with respect to the electric conductive polymer of 100 weight parts, the content of polyanion is that 10 to 200 weight parts and the content with the dispersion agent of branched structure are 1 to 120 weight part.More preferably, with respect to the electric conductive polymer of 100 weight parts, the content of polyanion is that 50 to 150 weight parts and the content with the dispersion agent of branched structure are 1 to 50 weight part.
Electric conductive polymer suspension preferably contains at least one water-soluble binder.The example of water-soluble binder comprises polyvinyl alcohol, polyacrylic acid, polyacrylamide, Polyvinylpyrolidone (PVP), polyester, urethane, polymeric amide, and the multipolymer that comprises these two or more structural units, and can select adopted water-soluble binder at the tackiness agent using for coated polymeric suspension.Wherein, what find is by adding carboxyl or sulfo group to it or being modified as water miscible polyester with polyoxyethylene glycol copolymerization or polymeric amide does not weaken dispersion of particles stability in electric conductive polymer suspension, and does not substantially affect the electric conductivity of the electroconductibility organic materials being obtained by electric conductive polymer suspension.
With respect to the electric conductive polymer of 100 weight parts, in electric conductive polymer suspension, the content of water-soluble binder is 10 to 400 weight parts.
Thereby add water-soluble binder to improve the adhesivity to base material.Electric conductive polymer suspension can be containing the linking agent that is useful on cross-linked, water-soluble tackiness agent together with water-soluble binder.
In order to improve the character of conductive polymer material, as electric conductivity, density, and the object of intensity, preferably mix electric conductive polymer suspension with tetrahydroxybutane and/or tetramethylolmethane.
Because higher on as the crystallinity of Sorbitol Powder and maltose alcohol than polyhydroxy-alcohol, tetrahydroxybutane is preferred, and therefore low in water absorbability and and easy handling.In addition, tetrahydroxybutane is known as the foodstuff additive for using as sweeting agent, is also outstanding on safety and stability.Tetrahydroxybutane is useful because the solubleness at it in water than non-aqueous solvent therefore as high several times in the solubleness of ethylene glycol and glycerine and its add-on can high freedom design.
Tetramethylolmethane be characterised in that along with heating with by little by little distillation together with for the temperature thermal dehydration that is equal to or higher than its fusing point of polymerization.As a result of, can acquire change the physical properties of conductive polymer material to improve the benefit of density and intensity.Therefore, be difficult to obtain this reactivity by structure as tetrahydroxybutane and Sorbitol Powder.
Tetrahydroxybutane has the effect of higher raising electric conductivity, and tetramethylolmethane has higher raising character as the effect of density and intensity.
Thereby at least one of tetrahydroxybutane and tetramethylolmethane mixed and represented effect to be equal to or higher than the concentration of the concentration of polymkeric substance in electric conductive polymer suspension with electric conductive polymer suspension.Here, the upper limit concentration of added amount is not particularly limited, condition is that tetrahydroxybutane and tetramethylolmethane are dissolved in electric conductive polymer suspension.
According to the conductive polymer material of embodiment of the present invention, by dry electric conductive polymer suspension, to remove solvent, obtain, and it is outstanding on to the adhesivity of base material and water tolerance, and high in electric conductivity.To being not particularly limited for removing the drying temperature of solvent, condition is the decomposition temperature that it is equal to or less than electric conductive polymer, but for preferably below 300 ℃.
<for the preparation of the method for electric conductive polymer suspension>
According to the method for the preparation of electric conductive polymer suspension of embodiment of the present invention, comprise following steps.
(first step)
In embodiments of the invention, first by use oxygenant contain organic acid or its salt as the solvent of doping agent in to for providing the monomer of electric conductive polymer to carry out chemical oxidising polymerisation so that the mixture that contains electric conductive polymer to be provided.In first step, can provide the electric conductive polymer with high-polymerization degree and high-crystallinity.
The example of doping agent comprises alkylsulphonic acid, Phenylsulfonic acid, naphthene sulfonic acid, anthraquinone sulfonic acid, camphorsulfonic acid, and their derivative, with and iron (III) salt.This sulfonic acid can be each single sulfonic acid, disulfonic acid or trisulfonic acid.The example of the derivative of alkylsulphonic acid comprises 2-acrylamide-2-methyl propane sulfonic.The example of the derivative of Phenylsulfonic acid comprises sulfocarbolic acid, styrene sulfonic acid, toluenesulphonic acids, and Witco 1298 Soft Acid.The example of the derivative of naphthene sulfonic acid comprises 1-naphthalene sulfonic aicd, 2-naphthene sulfonic acid, 1,3-naphthalene disulfonic acid, 1,3,6-naphthalene trisulfonic acid, and 6-ethyl-1-naphthalene sulfonic aicd.The example of the derivative of anthraquinone sulfonic acid comprises anthraquinone-1-sulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-2,6-disulfonic acid, and 2-methylanthraquinone-6-sulfonic acid.Wherein, 1-naphthalene sulfonic aicd, 2-naphthene sulfonic acid, 1,3,6-naphthalene trisulfonic acid, anthraquinone disulfonic acid, tosic acid, camphorsulfonic acid and its iron (III) salt are preferred.Camphorsulfonic acid is also preferred, because its large impact on the high crystalline of polymkeric substance.Camphorsulfonic acid can be photoactive.Can use one or more this doping agent.
Amount to used doping agent is not particularly limited, even because doping agent is excessive also can be removed in second step, but is preferably 1 to 100 weight part and more preferably 1 to 50 weight part with respect to the monomer of 1 weight part.
Any in the organic solvent that can make water, organic solvent and mix with water be as solvent, and be preferably chosen in the solvent first-class with mhc monomer.Particularly preferably be chosen in the consistency with doping agent and oxygenant might as well solvent.The example of organic solvent comprises that alcoholic solvent is as methyl alcohol, ethanol and propyl alcohol; With low polar solvent as acetonitrile, acetone and methyl-sulphoxide.Can use one or more this organic solvent.Wherein, the mixed solvent of ethanol or second alcohol and water is preferred.
Electric conductive polymer is preferably and comprises pyrroles, thiophene, and at least one polymkeric substance of their derivative.
Can depend on object electric conductive polymer selects for the monomer of electric conductive polymer is provided.Can use one or more monomers.
Derivative by the corresponding pyrroles of polymerization or pyrroles obtains polypyrrole and derivative thereof.The example of pyrroles's derivative comprises that 3-alkyl pyrroles is as 3-hexyl pyrroles, 3, and 4-dialkyl group pyrroles is if 3,4-dihexyl pyrroles, 3-alkoxyl group pyrroles are as 3-methoxyl group pyrroles, and 3,4-dimethoxy pyrroles is as 3,4-dimethoxy pyrroles.
Derivative by the corresponding thiophene of polymerization or thiophene obtains Polythiophene and derivative thereof.The example of the derivative of thiophene comprises 3,4-Ethylenedioxy Thiophene and derivative thereof, and 3-alkylthrophene is as 3-hexyl thiophene, and 3-alkoxy thiophene is as 3-methoxythiophene.The example of the derivative of 3,4-Ethylenedioxy Thiophene comprises that 3,4-(1-alkyl) Ethylenedioxy Thiophene is as 3,4-(1-hexyl) Ethylenedioxy Thiophene.
Wherein, poly-(3, the 4-Ethylenedioxy Thiophene) or derivatives thereof being represented by following formula (3) is preferred.
In solvent, the concentration of monomer is preferably 0.1 to 50 % by weight and more preferably 0.5 to 30 % by weight.
Oxygenant is not particularly limited, and iron (III) salt that the example of operable oxygenant comprises mineral acid is as iron(ic) chloride (III) hexahydrate, Anhydrous Ferric Chloride (III), iron nitrate (III) nonahydrate, anhydrous nitric acid iron, ferric sulfate (III) n-hydrate (n=3 to 12), ferric sulfate (III) ammonium dodecahydrate, Iron triperchlorate (III) n-hydrate (n=1,6) and Tetrafluoroboric acid iron (III); The copper of mineral acid (II) salt is as cupric chloride (II), copper sulfate (II) and Tetrafluoroboric acid copper (II); Tetrafluoroboric acid nitrous
; Persulphate is as ammonium persulphate, Sodium Persulfate and Potassium Persulphate; Periodate is as potassium periodate; Hydrogen peroxide, ozone, the sour potassium of six cyanogen iron (III), sulfuric acid four ammonium cerium (IV) dihydrates, bromine and iodine; With organic acid iron (III) salt as tosic acid iron (III).Wherein, mineral acid or organic acid iron (III) salt, or persulphate is that preferably ammonium persulphate or tosic acid iron (III) they are preferred.Tosic acid iron (III) is preferred, because it also has the function as doping agent.Can use one or more in this oxygenant.
Amount to used oxygenant is not particularly limited, even if because excessively also doping agent can be removed in second step.Yet in order to obtain the polymkeric substance with high conductivity by reaction under compared with mild oxidation atmosphere, the amount of the oxygenant adding is preferably 0.5 to 100 weight part and more preferably 1 to 50 weight part with respect to the monomer of 1 weight part.
Temperature of reaction to chemical oxidising polymerisation is not particularly limited, but it is typically about the reflux temperature of used solvent, and is preferably 0 to 100 ℃ and more preferably 10 to 50 ℃.If temperature of reaction is improper, there is the impaired situation of electric conductivity possibility.The reaction times of chemical oxidising polymerisation depends on type and amount, temperature of reaction or the agitation condition of packed into oxygenant.Reaction times can be approximately 5 to 100 hours.
First step preferably carries out under the existence of material with surface-active action.As the material with surface-active action, can use anion surfactant, cats product, or amphoterics.Witco 1298 Soft Acid or polyoxyethylene glycol are suitable.
(second step)
In embodiments of the invention, mixture electric conductive polymer being obtained from first step reclaims.Particularly, by electric conductive polymer is removed from the reaction solution that contains the electric conductive polymer obtaining by chemical oxidising polymerisation, and wash afterwards electric conductive polymer, by doping agent, unreacted monomer with come residual metal ion and the negatively charged ion of autoxidator to remove.By second step, can carry out enough purification process and there is highly purified electric conductive polymer to provide.
From the example of the method for the separated electric conductive polymer of reaction solution, comprise filtration method and centrifuging.
As cleaning solvent, preferably use can dissolved monomer and/or oxygenant and do not dissolve the solvent of electric conductive polymer.The example of cleaning solvent comprises water, and alcoholic solvent is as methyl alcohol, ethanol and propyl alcohol.Can use one or more this cleaning solvent.The degree of washing can wash by measurements after cleaning solvent pH or by carrying out colorimetric observation confirmation.
In addition, preferably electric conductive polymer is heat-treated with hot wash and/or to it, because can remove with higher level the metal component of autoxidator.Heat treated temperature is not particularly limited, and condition is the decomposition temperature that it is equal to or less than electric conductive polymer.Thermal treatment is preferably being carried out lower than 300 ℃.The ion exchange treatment that in addition, also can effectively make spent ion exchange resin is as for removing the method for metal ion and the negatively charged ion of autoxidator.
The impurity containing in electric conductive polymer can be carried out to quantitative analysis by ICP emission analysis or chromatography of ions.
(third step)
In embodiments of the invention, the electric conductive polymer reclaiming in second step is mixed in containing the aqueous solvent of polyanion with oxygenant.In third step, by allowing polyanion as dispersion agent and making oxygenant act on electric conductive polymer, obtain the wherein good electric conductive polymer suspension of dispersibility of electric conductive polymer.As dispersal mechanism, at least to consider the chanza owing to the negatively charged ion of polyanion.
As polyanion, can use above-mentioned polyanion.Especially, polystyrolsulfon acid is preferred.The weight-average molecular weight of polyanion is preferably 2,000 to 500,000 and more preferably 10,000 to 200,000.
With respect to the electric conductive polymer obtaining in second step of 100 weight parts, the amount of the polyanion using is preferably 10 to 200 weight parts and more preferably 50 to 150 weight parts.
As oxygenant, can use the oxygenant identical with the oxygenant using in first step, and especially, ammonium persulphate or hydrogen peroxide are preferred.
The electric conductive polymer obtaining in second step with respect to 100 weight parts, the amount of the oxygenant using is preferably 10 to 500 weight parts and more preferably 50 to 300 weight parts.
Aqueous solvent is preferably water, but water-miscible organic solvent can be added wherein and without any problem.As water-miscible organic solvent, when being added to water when using, can select and use to be suitable for a kind of of oxidizing reaction.Except this requirement, when by the liquid of the mixing obtaining in third step during in statu quo for the 4th step, can preferably select and use can be as the organic solvent of the solvent (liquid medium) of the electric conductive polymer suspension that finally will obtain.The example of this organic solvent comprises that alcoholic solvent is as methyl alcohol, ethanol and propyl alcohol; With low polar solvent as acetonitrile, acetone and methyl-sulphoxide.Can use one or more this organic solvent.
Temperature of reaction in third step is not particularly limited, but it is preferably 0 to 100 ℃ and more preferably 10 to 50 ℃.Reaction times is not particularly limited, but it is approximately 5 to 100 hours.In addition, above-mentioned ion exchange treatment is preferably carried out after third step.
(the 4th step)
In embodiments of the invention, by after thering is the dispersant of branched structure, by electric conductive polymer efflorescence.By after thering is the dispersant of branched structure, by electric conductive polymer efflorescence, thereby make to provide the electric conductive polymer suspension with high dispersion stability.Efflorescence in the 4th step is efflorescence electric conductive polymer at least in part, that is, also can be partially or completely by electric conductive polymer efflorescence to 100nm.
The electric conductive polymer obtaining in second step with respect to 100 weight parts, the amount of the dispersion agent with branched structure using is preferably 1 to 120 weight part and more preferably 1 to 50 weight part.
In the process of the 4th step or preferably mix afterwards one or more water-soluble binders.As water-soluble binder, can use above-mentioned tackiness agent.Wherein, by adding carboxyl or sulfo group to be modified as water miscible polyester or polymeric amide is particularly preferred.
With respect to the electric conductive polymer of 100 weight parts, in electric conductive polymer suspension, the content of water-soluble binder is 10 to 400 weight parts.
Can be preferably in the process of the 4th step or mix afterwards tetrahydroxybutane and/or tetramethylolmethane.For the amount of added tetrahydroxybutane and/or tetramethylolmethane, tetrahydroxybutane and/or tetramethylolmethane can be mixed to be equal to or higher than the concentration of the concentration of polymkeric substance in electric conductive polymer suspension, thereby represent required effect.Upper limit concentration to added amount is not particularly limited, and condition is tetrahydroxybutane and/or tetramethylolmethane can be dissolved in electric conductive polymer suspension.
More than thereby the water content in the electric conductive polymer suspension obtaining is preferably 50 % by weight.
<electrolytic condenser and preparation method thereof>
According to the electrolytic condenser of embodiment of the present invention, comprise conductive polymer material as dielectric substrate, it is obtained by above electric conductive polymer suspension.Dielectric substrate is the form of preferred solid.Low on ESR according to the electrolytic condenser of embodiment of the present invention, because it is high in electric conductivity to be used to form electrolytical material.In addition, polymer materials high in degree of crystallinity is also high in the oxygen barrier relevant to high-crystallinity, and also outstanding on to the adhesivity of base material owing to adhesive effect.As a result of, expect that fully the reliability of electrolytic condenser can improve.
Fig. 1 shows signal according to the schematic section of the structure of the solid electrolytic capacitor of embodiment of the present invention.Electrolytic condenser is provided with wherein dielectric layer 2, and solid electrolyte layer 3 and cathode conductor 4 are formed on the structure on plate conductor 1 by above order.
The example that is used to form the method for solid electrolyte layer 3 comprises the method that comprises the following: with above-mentioned electric conductive polymer suspension coating or dipping dielectric layer 2, and remove solvent from electric conductive polymer suspension.In addition, solid electrolyte layer 3 in solid electrolytic capacitor shown in Fig. 1 can be by comprising that the method for the following forms: to for providing the monomer of the first electric conductive polymer compound to carry out chemical oxidising polymerisation or electropolymerization to form the first electric conductive polymer compound layer 3A on dielectric layer, and with above electric conductive polymer suspension coating or flood the first electric conductive polymer compound layer 3A to form the second electric conductive polymer compound layer on the first electric conductive polymer compound layer 3A.
For being selected from least one in the following for the monomer of the first electric conductive polymer compound being provided, can using: pyrroles, thiophene, aniline and derivative thereof.As the doping agent for when using when obtaining the chemical oxidising polymerisation of monomer of the first electric conductive polymer compound or electropolymerization, the compound based on sulfonic acid as Phenylsulfonic acid, naphthene sulfonic acid, sulfocarbolic acid, styrene sulfonic acid and their derivative be preferred.The molecular weight of can be in the scope from lower molecular weight to high molecular suitably selecting the doping agent that uses.Solvent can be only water, can be also water and in water the mixed solvent of soluble organic solvent.
Coating or dipping method are not particularly limited, but after coating or dipping preferably by standing several minutes to tens of minutes of electric conductive polymer suspension so that permission electric conductive polymer suspension is filled in the hole of porous material fully.The method is preferably passed through repeated impregnations, or is undertaken by depressurized system or compression system.
Solvent can be undertaken by dry electric conductive polymer from removing of electric conductive polymer suspension.Drying temperature is not particularly limited, and condition is that it is the temperature that can remove solvent, but from prevent element due to heat and deteriorated angle, ceiling temperature is preferably less than 300 ℃.Need to depend on drying temperature and suitably optimize needed time of drying, but be not particularly limited, condition is not affect electric conductivity.
Embodiment
Hereinafter, will describe embodiment of the present invention in detail based on embodiment, but the present embodiment is not intended to only limit to these embodiment.
(embodiment 1)
(first step)
Using as 3 of monomer, 4-Ethylenedioxy Thiophene (2g), as the camphorsulfonic acid (2g) of doping agent, and (18g) be dissolved in the ethanol (60ml) as solvent as the tosic acid iron (III) of oxygenant and doping agent.Resulting solution is at room temperature stirred to 24 hours to carry out the oxypolymerization of monomer.In this process, the color of mixing liquid is changed into mazarine from yellow.
(second step)
The mixing liquid obtaining in first step is filtered to reclaim powder by pressure-reducing filter.Resulting powder is washed to remove excessive oxygenant and doping agent with pure water.Repeat with the washing of pure water until the pH of filtrate reaches 6 to 7.At the pH of filtrate, reach 6 after 7, by powder further with washing with alcohol with reaction after remove monomer, oxygenant and oxygenant (tosic acid iron (II)).With ethanol, wash until the color of filtrate becomes colorless and be transparent.
(third step)
The powder washing in second step (1g) is dispersed in water (200ml), and the polystyrolsulfon acid (weight-average molecular weight: the aqueous solution 50,000) (0.5g) that adds afterwards the poly-acid of conduct (polyanion) of 20 % by weight to it.To the liquid mixing, further add the ammonium persulphate (1.5g) as oxygenant, and at room temperature stir 24 hours.The color of resulting Polythiophene suspension is navy blue.
(the 4th step)
The dispersion agent (DISPERBYK (R)-190, the 40 % by weight aqueous solution, BYK-Chemie GmbH) with branched structure (3g) is added to the mixing liquid obtaining in third step, and at room temperature stirs 1 hour to dissolve completely.Thereafter, by the particle in mixing liquid by using ball mill efflorescence so that median size is adjusted to 500nm.The hue preserving of resulting Polythiophene suspension is navy blue.
Use dynamic light scattering method (surveying instrument: Zeta-potential& Particle Size Analyzer ELSZ-2 (Otsuka Electronics Co., Ltd.)) for measuring median size.
(evaluation of Polythiophene suspension)
By resulting Polythiophene suspension with the minim of 100 μ l on glass baseplate, and its solvent is volatilized completely with dry to form electric conductive polymer film at 125 ℃ in thermostatic bath.
By four-terminal method, measure the surface resistivity (Ω/sq) of resulting electric conductive polymer film and thickness to calculate electric conductivity (S/cm).
(embodiment 2)
Except in third step, by added polystyrolsulfon acid (weight-average molecular weight: 50,000) amount of the 20 % by weight aqueous solution is changed into 5g, and in the 4th step, by the added dispersion agent with branched structure (DISPERBYK (R)-190, the 40 % by weight aqueous solution, BYK-Chemie GmbH) amount is changed into outside 0.2g, in mode in the same manner as in Example 1, prepares Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 3)
Except in third step, by added polystyrolsulfon acid (weight-average molecular weight: 50,000) amount of the 20 % by weight aqueous solution is changed into 10g, and in the 4th step, by the added dispersion agent with branched structure (DISPERBYK (R)-190, the 40 % by weight aqueous solution, BYK-Chemie GmbH) amount is changed into outside 0.04g, in mode in the same manner as in Example 1, prepares Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 4)
Except in third step, use the polystyrolsulfon acid of the weight-average molecular weight with 2,000 as outside poly-acid, in mode in the same manner as in Example 2, prepare Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 5)
Except in the 4th step, the particle in mixing liquid, by using ball mill efflorescence so that median size is adjusted to outside 50nm, is prepared to Polythiophene suspension in mode in the same manner as in Example 1.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 6)
Except in the 4th step, the particle in mixing liquid, by using ball mill efflorescence so that median size is adjusted to outside 50nm, is prepared to Polythiophene suspension in mode in the same manner as in Example 2.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 7)
Except in the 4th step, the particle in mixing liquid, by using ball mill efflorescence so that median size is adjusted to outside 50nm, is prepared to Polythiophene suspension in mode in the same manner as in Example 3.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 8)
Except after the 4th step, add water-soluble polyester (PESRESINA-610, the 25 % by weight aqueous solution, Takamatsu Oil& Fat Co., Ltd.) (8g) and at room temperature stir 1 hour with beyond dissolving completely, in mode in the same manner as in Example 2, prepare Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 9)
Except after the 4th step, add water soluble polyamide (AQ Nylon P-95, the 50 % by weight aqueous solution, Toray Industries Inc.) (4g), and by its stirring at room 1 hour with consoluet step by it outside, in mode in the same manner as in Example 2, prepare Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 10)
Except after the 4th step, add water-soluble polyester (PESRESIN A-610, the 25 % by weight aqueous solution, Takamatsu Oil& Fat Co., Ltd.) (8g) and tetrahydroxybutane (10g), and by its stirring at room 1 hour with consoluet step by it outside, in mode in the same manner as in Example 2, prepare Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 11)
Except after the 4th step, add water-soluble polyester (PESRESINA-610, the 25 % by weight aqueous solution, Takamatsu Oil& Fat Co., Ltd.) (8g) and tetramethylolmethane (10g), and by its stirring at room 1 hour with consoluet step by it outside, in mode in the same manner as in Example 2, prepare Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 12)
Except after the 4th step, add water-soluble polyester (PESRESIN A-610, the 25 % by weight aqueous solution, Takamatsu Oil& Fat Co., Ltd.) (8g), and by its stirring at room 1 hour with consoluet step by it outside, in mode in the same manner as in Example 6, prepare Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 13)
Except after the 4th step, add water soluble polyamide (AQ Nylon P-95, the 50 % by weight aqueous solution, Toray Industries Inc.) (4g), and by its stirring at room 1 hour with by its consoluet step, in mode in the same manner as in Example 6, prepare Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 14)
Except after the 4th step, add water-soluble polyester (PESRESIN A-610, the 25 % by weight aqueous solution, Takamatsu Oil& Fat Co., Ltd.) (8g) and tetrahydroxybutane (10g), and by its stirring at room 1 hour with consoluet step by it outside, in mode in the same manner as in Example 6, prepare Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 15)
Except after the 4th step, add water-soluble polyester (PESRESIN A-610, the 25 % by weight aqueous solution, Takamatsu Oil& Fat Co., Ltd.) (8g) and tetramethylolmethane (10g), and by its stirring at room 1 hour with consoluet step by it outside, in mode in the same manner as in Example 6, prepare Polythiophene suspension.Afterwards, except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(comparative example 1)
By the method for describing in the embodiment 1 of patent documentation 1, prepare Polythiophene suspension.Particularly, to have 4, the polystyrolsulfon acid of 000 weight-average molecular weight (2g), 3,4-Ethylenedioxy Thiophene (0.5g) and ferric sulfate (III) (0.05g) are dissolved in water (20ml), and in 24 hours, air are introduced into wherein to prepare Polythiophene suspension.
Except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(comparative example 2)
To have 4, the polystyrolsulfon acid of 000 weight-average molecular weight (12.4g), 3,4-Ethylenedioxy Thiophene (1.6g) and ferric sulfate (III) (0.16g) are dissolved in water (1000ml), and in 24 hours to its introducing air to prepare Polythiophene suspension.Thereafter, by Polythiophene suspension by using high-pressure homogenizer at 700 bar and with twice of the nozzle diameter homogenizing of 0.1mm.The median size of the particle in the aqueous solution is 20nm.
Except using resulting Polythiophene suspension, in mode in the same manner as in Example 1, form electric conductive polymer film, and evaluate its electric conductivity.Result provides in table 1.
(embodiment 16)
Use porous aluminum material as the plate conductor that comprises valve metal, and by anodic oxidation, form the oxide film that serves as dielectric layer on the surface of porous aluminum material.Anode segment and negative electrode section are separated by insulating resin.Afterwards, the negative electrode section of the plate conductor of upper formation dielectric layer is immersed in the Polythiophene suspension of preparing in embodiment 2 and pulls out from it, and in thermostatic bath, at 125 ℃, is dried and solidifies to form solid electrolyte layer afterwards.Afterwards, on solid electrolyte layer, in succession form graphite linings and argentiferous resin layer to prepare solid electrolytic capacitor.
By using electric capacity and the ESR (equivalent serial resistance) of the other resulting solid electrolytic capacitor of frequency measurement at 120Hz and 100kHz of LCR score.Electric capacity and ESR value are normalized to the (1cm of unit surface from those of whole negative electrode section areas
2) value.Result provides in table 2.
(embodiment 17)
In using embodiment 10, the Polythiophene suspension of preparation is used to form solid electrolyte layer, to prepare solid electrolytic capacitor with mode identical in embodiment 16, and evaluates its electric capacity and ESR.Result provides in table 2.
(embodiment 18)
Except using the Polythiophene suspension of preparation in embodiment 14 to be used to form solid electrolyte layer, to prepare solid electrolytic capacitor with mode identical in embodiment 16, and evaluate outside its electric capacity and ESR.Result provides in table 2.
(embodiment 19)
Use porous aluminum material as the plate conductor that comprises valve metal, and by anodic oxidation, form the oxide film that serves as dielectric layer on the surface of porous aluminum material.Anode segment and negative electrode section are separated by insulating resin.Afterwards, the negative electrode section of the plate conductor of upper formation dielectric layer in order repeated impregnations in monomer liquid and oxidant liquid and and from it, pull out ten times, to carry out chemical oxidising polymerisation, thereby form the first electric conductive polymer compound layer, wherein in described monomer liquid, pyrroles (10g) is dissolved in pure water (200ml), and in described oxidant liquid, using the tosic acid as doping agent (20g) with as the ammonium persulphate (10g) of oxygenant, be dissolved in pure water (200ml).
The Polythiophene hanging drop of preparation in embodiment 10 on the first electric conductive polymer compound layer and is afterwards dried and solidifies to form the second electric conductive polymer compound layer at 125 ℃ in thermostatic bath.Afterwards, graphite linings and argentiferous resin layer are formed on the solid electrolyte layer that comprises the first electric conductive polymer compound layer and the second electric conductive polymer compound layer, to prepare solid electrolytic capacitor in succession.
To evaluate electric capacity and the ESR of the solid electrolytic capacitor being obtained with mode identical in embodiment 16.Result provides in table 2.
(embodiment 20)
In using embodiment 14, the Polythiophene suspension of preparation is used to form solid electrolyte layer, to prepare solid electrolytic capacitor with mode identical in embodiment 19.To evaluate electric capacity and the ESR of the solid electrolytic capacitor being obtained with mode identical in embodiment 16.Result provides in table 2.
(comparative example 3)
In using comparative example 1, the Polythiophene suspension of preparation replaces the Polythiophene suspension of preparation in embodiment 2, to prepare solid electrolytic capacitor with mode identical in embodiment 16.To evaluate electric capacity and the ESR of the solid electrolytic capacitor being obtained with mode identical in embodiment 16.Result provides in table 2.
(comparative example 4)
In using comparative example 2, the Polythiophene suspension of preparation replaces the Polythiophene suspension of preparation in embodiment 2, to prepare solid electrolytic capacitor with mode identical in embodiment 16.To evaluate electric capacity and the ESR of the solid electrolytic capacitor being obtained with mode identical in embodiment 16.Result provides in table 2.
[table 1]
Table 1
In table 1, in the situation that median size is 500nm therein, do not comprise that its size is for the particle below 100nm.
[table 2]
Table 2
| ? | Electric capacity (μ Fcm 2) | ESR(mΩ·cm 2) |
| Embodiment 16 | 201 | 1.4 |
| Embodiment 17 | 203 | 1.2 |
| Embodiment 18 | 219 | 1.3 |
| Embodiment 19 | 207 | 1.3 |
| Embodiment 20 | 211 | 1.2 |
| Comparative example 3 | 200 | 3.5 |
| Comparative example 4 | 209 | 1.8×10 3 |
As shown in table 1, the electric conductivity of each of the electric conductive polymer film obtaining in embodiment 1 to 15 is higher than each electric conductivity of the electric conductive polymer film obtaining in comparative example 1 and 2.In other words, according to the effect of the increase electric conductivity of embodiment of the present invention, be significant.Especially, even in the situation that the particle diameter of electric conductive polymer is partly or wholly for (in the situation that median size is 50nm) below 100nm in electric conductive polymer suspension, it is significant also obtaining electric conductive polymer film and its effect with high conductivity.
The effect that increases electric conductivity is owing to the following: according to the electric conductive polymer suspension of embodiment of the present invention, contain electric conductive polymer, and at least one polyanion, and at least one has the dispersion agent of branched structure.
According to above composition, outstanding in the dispersion of particles stability that electric conductive polymer suspension contains therein.Therefore, can reduce the polyanion that is not used as doping agent and does not contribute to electric conductivity with respect to electric conductive polymer, and the electroconductibility organic materials being obtained by electric conductive polymer suspension is high in electric conductivity.
The electric conductivity of each of the electric conductive polymer film obtaining in embodiment 2,4,6 and 8 to 15 is higher than each electric conductivity of the electric conductive polymer film obtaining in embodiment 1,3,5 and 7.Reason be because the polyanion containing in each of the electric conductive polymer suspension of embodiment 2,4,6 and 8 to 15 and there is the dispersion agent of branched structure and each of the electric conductive polymer suspension of the ratio of electric conductive polymer in each of embodiment 1,3,5 and 7 in described ratio low.
In addition, method for the preparation of electric conductive polymer suspension experiences first step to third step, and the doping agent that can select for increasing degree of crystallinity is expanded as in the selection of (thereby 1) doping agent, (2) can select to have with the solvent compositions of the high-compatibility of monomer can increase the polymerization degree, and the easiness of (3) washing can increase purity to produce the increase in electric conductivity.
In addition, thus in the process of the 4th step or add afterwards tetrahydroxybutane to improve electric conductivity.Its reason is because tetrahydroxybutane and negatively charged ion interact, thereby reduce the resistance between electric conductive polymer particle and increase the density of electric conductive polymer, described negatively charged ion is not used as doping agent (as resistance component), and its electric conductive polymer particle in electric conductive polymer suspension near existence and adding in third step.
Even in the process of the 4th step or add afterwards the water-soluble binder that comprises polyester or polymeric amide, electric conductivity is also influenced hardly.
As shown in table 2, the resistance (ESR) of each solid electrolytic capacitor obtaining in embodiment 16 to 20 is lower than the resistance of each solid electrolytic capacitor obtaining in comparative example 3 to 4.In each of embodiment 16 to 20, the electric conductivity of the electroconductibility organic materials using is high.Therefore, the resistance of solid electrolyte can reduce and resistance (ESR) also can reduce.Even if the particle diameter of the electric conductive polymer in electric conductive polymer suspension is partly or wholly in the situation below 100nm therein, also obtain at the upper low solid electrolytic capacitor of resistance (ESR), and therefore effect is significant.In addition, wherein the particle diameter of electric conductive polymer is partly or wholly for electric conductive polymer suspension below 100nm is suitable for forming electroconductibility organic materials in the hole of the porous material of the plate conductor as comprising valve metal, and outstanding on capacitive property.
Reference numeral
1 plate conductor
2 dielectric layers
3 solid electrolyte layers
3A the first electric conductive polymer compound layer
3B the second electric conductive polymer compound layer
4 cathode conductors
5 carbon-coatings
6 silver medal conductive resin layers
Claims (35)
1. an electric conductive polymer suspension, described electric conductive polymer suspension comprises electric conductive polymer, at least one polyanion, and at least one has the dispersion agent of branched structure.
2. electric conductive polymer suspension according to claim 1, wherein said electric conductive polymer comprises the electric conductive polymer with the particle diameter below 100nm.
3. electric conductive polymer suspension according to claim 1, the particle diameter of wherein said electric conductive polymer is below 100nm.
4. according to the electric conductive polymer suspension described in any one in claims 1 to 3, the wherein said dispersion agent with branched structure comprises lower array structure, described structure is with and is useful on the adsorption group that is adsorbed to described electric conductive polymer in main chain, and described structure is with one or more wetting abilities and/or hydrophobic side chains.
5. according to the electric conductive polymer suspension described in any one in claim 1 to 4, wherein with respect to the described electric conductive polymer of 100 weight parts, the amount of described polyanion is 10 to 200 weight parts, and described in there is the dispersion agent of branched structure amount be 1 to 120 weight part.
6. according to the electric conductive polymer suspension described in any one in claim 1 to 5, wherein said electric conductive polymer is at least one the polymkeric substance comprising in pyrroles, thiophene and their derivative.
7. according to the electric conductive polymer suspension described in any one in claim 1 to 5, described electric conductive polymer suspension contains polystyrolsulfon acid as described polyanion.
8. electric conductive polymer suspension according to claim 7, the weight-average molecular weight of wherein said polystyrolsulfon acid is 2,000 to 500,000.
9. according to the electric conductive polymer suspension described in any one in claim 1 to 8, described electric conductive polymer suspension comprises at least one water-soluble binder.
10. electric conductive polymer suspension according to claim 9, wherein said water-soluble binder is at least one in polyester and polymeric amide.
11. according to the electric conductive polymer suspension described in claim 9 or 10, and wherein, with respect to the described electric conductive polymer of 100 weight parts, the amount of described at least one water-soluble binder is 10 to 400 weight parts.
12. according to the electric conductive polymer suspension described in any one in claim 1 to 11, and described electric conductive polymer suspension comprises tetrahydroxybutane and/or tetramethylolmethane.
13. 1 kinds of methods for the preparation of electric conductive polymer suspension, described method comprises:
First step, by using oxygenant to for providing the monomer of electric conductive polymer to carry out chemical oxidising polymerisation in containing organic acid or the solvent of its salt as doping agent, so that the mixture that contains electric conductive polymer to be provided,
Second step, reclaims described electric conductive polymer from described mixture,
Third step mixes with described electric conductive polymer oxygenant in containing the aqueous solvent of polyanion, and
The 4th step, mixes and to have the dispersion agent of branched structure and afterwards to described electric conductive polymer efflorescence.
14. methods for the preparation of electric conductive polymer suspension according to claim 13, wherein said is at least one monomer that is selected from pyrroles, thiophene and their derivative for the monomer of electric conductive polymer is provided.
15. according to the method for the preparation of electric conductive polymer suspension described in claim 13 or 14, and wherein said doping agent is to be selected from least one of the following: Phenylsulfonic acid, naphthene sulfonic acid, camphorsulfonic acid and their derivative, and their salt.
16. according to claim 13 to the method for the preparation of electric conductive polymer suspension described in any one in 15, and wherein said first step carries out under the existence of material with surface-active action.
17. according to claim 13 to the method for the preparation of electric conductive polymer suspension described in any one in 16, wherein in described second step, by the solvent wash that can dissolve described monomer and/or described oxygenant for described electric conductive polymer.
18. according to claim 13 to the method for the preparation of electric conductive polymer suspension described in any one in 17, wherein, in described third step, uses polystyrolsulfon acid as described polyanion.
19. methods for the preparation of electric conductive polymer suspension according to claim 18, the weight-average molecular weight of wherein said polystyrolsulfon acid is 2,000 to 500,000.
20. according to claim 13 to the method for the preparation of electric conductive polymer suspension described in any one in 19, wherein in described the 4th step, by described electric conductive polymer efflorescence so that the electric conductive polymer particle that described electric conductive polymer comprises the particle diameter having below 100nm.
21. according to claim 13 to the method for the preparation of electric conductive polymer suspension described in any one in 19, wherein in described the 4th step, by described electric conductive polymer efflorescence so that its particle diameter is below 100nm.
22. according to claim 13 to the method for the preparation of electric conductive polymer suspension described in any one in 21, the wherein said dispersion agent with branched structure is provided with lower array structure, described structure is with and is useful on the adsorption group that is adsorbed to described electric conductive polymer in main chain, and described structure is with one or more wetting abilities and/or hydrophobic side chains.
23. according to claim 13 to the method for the preparation of electric conductive polymer suspension described in any one in 22, wherein with respect to the described electric conductive polymer of 100 weight parts, the amount of described poly-acid is 10 to 200 weight parts, and described in there is the dispersion agent of branched structure amount be 1 to 120 weight part.
24. according to claim 12 to the method for the preparation of electric conductive polymer suspension described in any one in 21, wherein in the process of described the 4th step or afterwards, mixes at least one water-soluble binder.
25. methods for the preparation of electric conductive polymer suspension according to claim 24, wherein said water-soluble binder is at least one in polyester and polymeric amide.
26. according to the method for the preparation of electric conductive polymer suspension described in claim 24 or 25, wherein, with respect to the described electric conductive polymer of 100 weight parts, with the amount of 10 to 400 weight parts, mixes described at least one water-soluble binder.
27. according to claim 13 to the method for the preparation of electric conductive polymer suspension described in any one in 26, wherein in the process of described the 4th step or afterwards, mixes tetrahydroxybutane and/or tetramethylolmethane.
28. 1 kinds of electric conductive polymer suspension, described electric conductive polymer suspension obtains by the method described in any one according to claim 13 in 27.
29. 1 kinds of conductive polymer materials, described conductive polymer material forms to remove described solvent according to the electric conductive polymer suspension described in any one in claim 1 to 12 and claim 28 by dry.
30. 1 kinds of electrolytic condenser, described electrolytic condenser comprises dielectric substrate, and described dielectric substrate comprises conductive polymer material according to claim 29.
31. electrolytic condenser according to claim 30, described electrolytic condenser comprises the plate conductor that comprises valve metal, and the dielectric layer forming on the surface of described plate conductor, wherein on described dielectric layer, forms described dielectric substrate.
32. 1 kinds of methods for the preparation of electrolytic condenser, described method comprises:
On the surface of the plate conductor that comprises valve metal, form the step of dielectric layer, and
With being coated with or flooding described dielectric layer to form the step of dielectric substrate on described dielectric layer according to the electric conductive polymer suspension described in any one in claim 1 to 12 and claim 28.
33. 1 kinds of methods for the preparation of electrolytic condenser, described method comprises:
On the surface of the plate conductor that comprises valve metal, form the step of dielectric layer,
To for providing the monomer of the first electric conductive polymer compound to carry out chemical oxidising polymerisation or electropolymerization to form the step of the first electric conductive polymer compound layer on described dielectric layer, and
With being coated with or flooding described the first electric conductive polymer compound layer to form the step of the second electric conductive polymer compound layer on described the first electric conductive polymer compound layer according to the electric conductive polymer suspension described in any one in claim 1 to 12 and claim 28.
34. methods for the preparation of electrolytic condenser according to claim 33, wherein said the first electric conductive polymer compound is at least one the polymkeric substance being selected from pyrroles, thiophene, aniline and their derivative.
35. according to the method for the preparation of electrolytic condenser described in any one in claim 32 to 34, and wherein said valve metal is at least one valve metal being selected from aluminium, tantalum and niobium.
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| JP2011110636A JP5441952B2 (en) | 2011-05-17 | 2011-05-17 | Conductive polymer suspension and method for producing the same, conductive polymer material, and electrolytic capacitor and method for producing the same |
| JP2011-110636 | 2011-05-17 | ||
| PCT/JP2012/062603 WO2012157693A1 (en) | 2011-05-17 | 2012-05-17 | Conductive polymer suspension and method for producing same, conductive polymer material, and electrolytic capacitor and method for producing same |
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| CN103534318A true CN103534318A (en) | 2014-01-22 |
| CN103534318B CN103534318B (en) | 2016-09-28 |
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| US (1) | US9455092B2 (en) |
| JP (1) | JP5441952B2 (en) |
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| US20140211372A1 (en) | 2014-07-31 |
| US9455092B2 (en) | 2016-09-27 |
| WO2012157693A1 (en) | 2012-11-22 |
| JP2012241068A (en) | 2012-12-10 |
| JP5441952B2 (en) | 2014-03-12 |
| DE112012002130T5 (en) | 2014-04-03 |
| CN103534318B (en) | 2016-09-28 |
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